JPH02275867A - Novel isocyanurate derivative - Google Patents

Abstract

NEW MATERIAL:An isocyanurate derivative expressed by the formula (either one of X1 and X2 is R1COO and other is OH; either one of Y1 and Y2 is R2COO and other is OH; either one of 21 and 22 is R3COO and other is OH; R1, R2 and R3 are OH or 1 to 20C alkyl which may be replaced by COOH). USE:Useful as a modifier of resin such as polyester or urethane resin produced by utilizing reaction of a hydroxyl group with other substituent group, curing agent or metal surface treating agent for epoxy resin, dispersing agent for inorganic powder, modifier for acryl rubber, etc. PREPARATION:Tris-(2,3-epoxypropyl)-isocyanurate is reacted with a carboxylic acid, e.g. in an organic solvent in the presence of a catalyst at 60 to 150 deg.C to provide the compound expressed by the formula.

Description

[Detailed Description of the Invention] Conventionally, as an isocyanurate compound, tris-(2-hydroxyethyl), which is used for heat-resistant enamel, etc.
-Isocyanurate (hereinafter referred to as THEIC), tris-(2,3-epoxypropyl)-isocyanurate (hereinafter referred to as TEPrC) used in powder coatings, etc., tris-(2-carboxyethyl)- Isocyanurate (hereinafter referred to as TCEIC), triallylisocyanurate, trichloroisocyanurate, and the like are known.

Common features of isocyanurate compounds and derivatives using these as starting materials include good weather resistance and transparency, and these properties are thought to be derived from the triazine skeleton.

For this reason, development of isocyanurate compounds and derivatives using them as starting materials has been carried out for a long time.

For example, derivatives using THEIC as a starting material include compounds such as esters with monocarboxylic acids;
As derivatives using IC as a starting material, compounds such as esters with alcohols are known, and attempts have been made to apply these to heat-resistant desensitizers and the like.

In addition, TEPr, an epoxy compound with high reactivity,
There are many examples in which C is used as a starting material.

Among epoxy compounds, TEPIC is well known to have particularly excellent heat resistance and weather resistance when cured, but it also has the problem of poor solvent solubility. 61374, Special public service 1974-374
94, etc., various carboxylic acids, amines, mercaptan compounds, etc., and 3 in the TEPIC molecule.
Research on derivatives has been conducted in an attempt to produce new epoxy compounds by reacting some of the existing epoxy groups.

Now, as isocyanurate compounds such as polyhydric alcohols having three or more hydroxyl groups in the molecule,
THEIC listed above is a representative compound of this type, but T
Although HEIC has excellent heat resistance and weather resistance, it has strong crystallinity, a high melting point, and although it is easily soluble in highly polar solvents such as alcohol and water, it is difficult to dissolve in ordinary organic solvents. There was also the problem that its uses were limited due to these properties.

Therefore, there has been a demand for isocyanurate compounds such as polyhydric alcohols that have low crystallinity and are easily soluble in common organic solvents.

As a result of intensive study, the inventor of the present application found the following formula (1) (wherein,
One of + and X2 is R, COO group and the other is OH group, and one of Yl and Y2 is R,
It is an isocyanurate derivative in which one of Z, Z, and t is an R, COO group and the other is an OH group, and R,, R2, and R1 are O
1 carbon number which may be substituted with H group or 000 group
It has been found that the above problems can be solved by producing a novel isocyanurate derivative represented by (~20 alkyl groups).

The isocyanurate derivative of the present invention has crystallinity of THE
It has become clear that the I C becomes lower than that of the I C and generally becomes amorphous, thereby improving solvent solubility.

Although the reason for this is not necessarily clear, it is presumed that the three fatty acid ester groups in the molecule inhibit its crystallinity.

The novel isocyanurate derivative of the present invention can be produced by reacting TEPIC with a carboxylic acid.

When producing the novel isocyanurate derivative of the present invention by reacting TEPIC with a carboxylic acid, the reaction conditions may be heating using a common organic solvent, or melting without using an organic solvent. Alternatively, carboxylic acid may be added to TEPIC.

Further, a catalyst that promotes the addition reaction of epoxy/carboxylic acid such as a quaternary ammonium salt, a tertiary amine, or an organic phosphorus compound may be added.

Further, the reaction temperature is not particularly limited, but it is preferably about 60-150°C when the reaction is carried out using an organic solvent with the addition of a catalyst, and about 100-200°C when using TEPIC melted without using an organic solvent. 'C rank is desirable.

Generally, the reaction product of an epoxy group and a carboxylic acid has the formula (
It is known that two types of isomers having different positions of the OH group and the ester group are produced as shown in formula (II) and formula (II[).

[Margin below]

0 [■] 0 [■] Therefore, although the derivative of the present invention is an adduct of carboxylic acid to the three epoxy groups of TEPIC, a total of 8 types of isomers are generated even when one type of carboxylic acid is used. .

Although these can be separated using high performance liquid chromatography equipment, column chromatography equipment, etc.
There are problems with low recovery rates.

However, since the isomers of the adduct of TEPIC and carboxylic acid have almost the same properties, there is no problem even if the isomers are a mixture even if they are not particularly separated.

Applications of the novel isocyanurate derivatives described in the claims include modification of resins produced by utilizing the reaction between hydroxyl groups and other substituents such as polyester and urethane resins, curing agents for epoxy resins, and metals. surface treatment agent,
Examples include dispersants for inorganic powders and modifiers for acrylic rubber.

Hereinafter, examples will be shown and explained in more detail.

4. Example <Example 1> In a four-loaf flask equipped with a stirrer, thermometer, and cooling tube, a T
EPIC-3 (trade name manufactured by Kagaku Kagaku Kogyo, Tris-(2,
3-Epoxyprobyl)-isocyanurate <TEPI
Add 297 parts by weight of high purity product of C> and 214 parts by weight of ethylene dichloride (hereinafter referred to as EDC), and
Dissolve at 0°C.

To this, 220 parts by weight of acetic acid and 2.3 parts by weight of tetramethylammonium chloride (hereinafter referred to as TMAC) as a reaction catalyst are added, and the mixture is reacted for 12 hours at the reflux temperature of EDC.

Thereafter, EDC and unreacted acetic acid were distilled off using an evaporator to obtain a starch syrup-like product.

By the above method, one of X and Xz is CH,
One is a COO group, the other is an OH group, and Y.

and Y2, one is CH, COO group and the other is O
H group, and one of Zl and Z2 is CHI
A target product was obtained in which one group was COO and the other was OH group.

As a result of measuring the epoxy value by perchloric acid titration, the amount of residual epoxy was below the detection limit of titration.

Shimadzu GPC columns H3G-15 and H3C;-
30, column temperature 40"C, eluent tetrahydrofuran, flow rate 1.8 m I 7 minutes, GPC
As a result of the compositional analysis of a 2% tetrahydrofuran solution of the product using the method, a single peak was observed at a retention time of 27.8 minutes.

The OH group content was measured by back titration after treatment with acetic anhydride and was found to be 6.2 equivalents/kg, which was almost in line with the theoretical value.

The results of infrared absorption spectrum measurement are shown in Table-1.

Absorption of an esterified carboxyl group generated around 1733 cm-' and an OH group generated around 3430 to 3450 cm-' was observed.

<Example 2> In the same manner as in Example 1, this time without using a solvent or catalyst, parts by weight of TEPIC-3297 were melted at 140"C, and then the temperature was lowered to 130°C and stirred. , 180 parts by weight of acetic acid is added thereto over 30 minutes to 1 hour, and then reacted for 2 hours.

Next, the temperature was raised to 140°C and the reaction was carried out for 1 hour.

After the reaction was completed, the mixture was cooled to obtain a starch syrup-like product.

By the above method, one of X and X2 is CH,
one is a COO group and the other is an OH group; one of Y+ and Y2 is a CH, COO group and the other is an OH group,
In addition, a target product was obtained in which one of Zl and Z2 was a CH, COO group and the other was an OH group.

As a result of measuring the epoxy value, it was below the detection limit.

As a result of the compositional analysis of the tetrahydrofuran solution of the product using the GPC method, the retention time was 27.8.
A single peak was observed at 10 min.

As a result of measuring the OH group content, it was 6.3 equivalent/kg, which was almost in line with the theoretical value.

The results of infrared absorption spectrum measurement are shown in Table-1.

Absorption of esterified carboxyl group generated around 1733 cm-' and OH5 generated around 3430-3450 cm-' was observed.

<Example 3> In the same manner as in Example 2, parts by weight of TEPIC-3297 were melted at 140°C, the temperature was lowered to 130°C and stirred, and 600 parts by weight of lauric acid was added thereto. In addition, the reaction was carried out at a temperature of 130'C for 2 hours, and then TM
3 parts by weight of AC was added and reacted for 2 hours to obtain a waxy product.

By the above method, one of xl and Xl is C,,H
, , COO group and the other is OH group, Y.

and Y! One of them is CIIH! 3000 groups, the other is OH5, and one of Zl and Z2 is C
A target product having +tHzCOO group and the other OH group was obtained.

The epoxy value was below the detection limit.

As a result of analyzing the composition of a 2% tetrahydrofuran solution of the product using the GPC method, the retention time was 25.
．． A single peak was observed at 6 minutes.

As a result of measuring the 01-1 group content, it was 3.3! /kg, which was in line with the theoretical value.

The results of infrared absorption spectrum measurement are shown in Table-1.

Absorption of an esterified carboxyl group generated around 1738 cm-' and an OH group generated around 3430-3450 cm-' was observed.

<Example 4> In the same manner as in Example 2, parts by weight of TEPIC-3297 were melted at 140"C, 852 parts by weight of stearic acid was added, and the mixture was reacted at a temperature of 140°C for 2 hours, and then TMAC3 Parts by weight were added and reacted for 2 hours to obtain a waxy product.

By the above method, one of X and X is CIt
H3s is a COO group and the other is an OH group, and one of Yl and Y2 is a C,,H,COO group and the other is an OH group.
group, and one of Zl and Z2 is CI? H
A target product was obtained in which one of the two groups was Y, 000 and the other was an OH group.

The epoxy value was below the detection limit.

As a result of analyzing the composition of a 2% tetrahydrofuran solution of the product using the GPC method, the retention time was 24.
．． A single peak was observed at 8 minutes.

The OH group content was measured to be 2.5 equivalents/kg, which was in line with the theoretical value.

The results of infrared absorption spectrum measurement are shown in Table-1.

Absorption of an esterified carboxyl group generated near 1739 cm-' and an OH group generated near 3430 to 3450 cm-' was observed.

<Example 5> In the same manner as in Example 2, parts by weight of TEP I C-3297 were melted at 140°C, the temperature was lowered to 110°C and stirred, and 348 parts by weight of caproic acid was added. hand,
The mixture was reacted for 3 hours, and then 3 parts by weight of TMAC was added, and the reaction was continued for 2 hours at a temperature of 130°C to obtain a starch syrup-like product.

By the above method, one of X and X2 is Cs H
+r is a COO group and the other is an OH group, one of Yl and Yt is a Cs Hl+ COO group and the other is an OH group, and one of Zl and Z2 is a C
, H,, a target product was obtained in which one group was COO and the other was OH group.

The epoxy value was below the detection limit.

As a result of analyzing the composition of a 2% tetrahydrofuran solution of the product using the GPC method, the retention time was 26.
．． A single peak was observed at 8 minutes.

The OH group content was measured to be 4.5 equivalents/kg, which was in line with the theoretical value.

The results of infrared absorption spectrum measurement are shown in Table-1.

Absorption of an esterified carboxyl group generated around 1739 cm'' and an OH group generated around 3430 to 3450 cm-' was observed.

<Example 6> In the same manner as in Example 2, parts by weight of TEP I C-3297 were melted at 140°C, the temperature was lowered to 110°C and stirred, and 222 parts by weight of propionic acid was melted. After that, 3 parts by weight of TMAC was added and the reaction was continued for 2 hours at a temperature of 130° C. to obtain a starch syrup-like product.

By the above method, one of XI and XO is converted to C, l(
, one is a COO group, the other is an OH group, and Y.

and Y2, one is a Cz Hs C00 group and the other is an OH group, and one of Zl and ZO is C
, H, COO groups and the other one was an OH group.

The epoxy value was below the detection limit.

The OH group content was measured to be 5.7 equivalents/kg, which was in line with the theoretical value.

The results of infrared absorption spectrum measurement are shown in Table-1.

Absorption of an esterified carboxyl group generated around 1735 cm-1 and an OH group generated around 3430 to 3450 cm-' was observed.

<Example 7> In the same manner as in Example 2, parts by weight of TEP I C-3297 were melted at 140°C, the temperature was lowered to 110°C and stirred, and 432 parts by weight of caprylic acid was melted. The mixture was added and reacted for 3 hours, and then 3 parts of TMAC was added and reacted for 2 hours at a temperature of 130°C to obtain a starch syrup-like product.

By the above method, one of xl and X2 is C1H1
sC00 group, the other is OH group, and Y.

and Y2, one is a C, H,, COO group, the other is an OH group, and one of Zl and Zt is C?
A target product was obtained in which one of the Hr s C00 groups and the other one was an OH group.

The epoxy value was below the detection limit.

As a result of measuring the OH group content, it was 4.0 equivalent/kg, which was almost in line with the theoretical value.

The results of infrared absorption spectrum measurement are shown in Table 1.

Absorption of an esterified carboxyl group generated around 1739 cm-' and an OH group generated around 3430-3450 cm-' was observed.

<Example 8> In the same manner as in Example 2, parts by weight of mEPIc-375 were melted at 140°C, the temperature was raised to 160°C, 5 parts by weight of lauric acid was added thereto, and the temperature was raised to 160°C. React at C for 3 hours.

Next, 200 parts by weight of ethyl acetate was added and washed at room temperature with stirring, and unreacted TEP I C was filtered off.

From the obtained filtrate, the solvent was distilled off under reduced pressure to obtain 19.63 parts by weight of a waxy product.

Next, 10 parts by weight of such waxy product and 4 parts by weight of acetic acid
The weight part was heated to 110″C for 2 hours, and then further heated to 140°C.
Allow to react for 1 hour.

The obtained starch syrup-like product was dissolved in 50 parts by weight of ethyl acetate, and washed thoroughly with water using a separating funnel to react the unreacted acetic acid and TEPIC remaining in the wax-like product with acetic acid. Product was removed.

Thereafter, the solvent was distilled off under reduced pressure to obtain a starch syrup-like product.

By the above method, one of Xl and X2 is made of Cr.
r Ht 2 is a COO group, the other is an OH group, and Y
.

and Y: one is CH, COO group and the other is OH
a group, and Zl and Z! One of them is CH, C
A target product was obtained in which one was an OO group and the other was an OH group.

The epoxy value was below the detection limit.

As a result of measuring the OH group content, it was 4.1 equivalent/kg, which was almost in line with the theoretical value.

The results of infrared absorption spectrum measurement are shown in Table-1.

Absorption of an esterified carboxyl group generated around 1738 cm-' and an OH group generated around 3430-3450 cm-' was observed.

<Example 9> In the same manner as in Example 2, parts by weight of TEPIC-3297 were melted at 140°C, the temperature was lowered to 130″C and stirred, 270 parts by weight of lactic acid was added, and the temperature was lowered. 130
The mixture was allowed to react at °C for 2 hours, and then 1.5 parts by weight of TMAC was added and allowed to react for 1 hour to obtain a starch syrup-like product.

By the above method, one of XI and X2 is CI?
Hss is a COO group and the other is an OH group, one of Yl and Y is a CH, COO group and the other is OH5, and one of Zl and z2 is CH, COO
The target product was obtained in which one group was one group and the other was an OH group.

The epoxy value was below the detection limit.

As a result of measuring the OH group content, it was 10.7 equivalent/kg, which was almost in line with the theoretical value.

The results of infrared absorption spectrum measurement are shown in Table-1.

Absorption of an esterified carboxyl group generated around 1743 cm-' and an OH group generated around 3430 to 3450 cm-1 was observed.

Table-1 Infrared absorption spectrum

Claims (1)

[Claims] The following general formula▲ includes mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, one of X_1 and X_2 is R_1
One of Y_1 and Y_2 is an R_2COO group and the other is an OH group, and one of Z_1 and Z_2 is an R_3COO group.
and the other is an OH group, and R_1, R_2, and R_3 are alkyl groups having 1 to 20 carbon atoms which may be substituted with an OH group or a COOH group. .